Capryldintrophenyl crotonate



Patented Oct. 24, 19$) CAPRYLDINITROPHENYL CROTONATE William F. Hester," Drexel Hill, and W E Craig, Philadelphia, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application July 6, 1946,

' Serial No. 681,764

1 Claim.

I r 1 This invention relates to parasiticidal compositions comprising capryldinitrophenyl crotonate, as the active parasiticidal or toxic agent, together with a carrier therefor. The compositions of this invention are effective against fungi, on the one hand, and against both chewing and sucking insects, on the other. They are, thus, highly valuable and useful in providing actions in a single spray or dust which are ordinarily obtained only 'by combining a variety of different insecticidal.

:and fungicidal agents or by the application of a :series of insecticidal and fungicidal compositions.

' To nitrophenols are attributed toxic properties which, it has been hoped, might prove useful for the-control ;of insects. Yet the usual dusts or aqueous suspensions of such phenols have caused severe injury to green plants. Hence, many variations in compound and type of application have been tried, yet without successful utili'zationof the indicated potentialities of this class of compounds. Furthermore, the phenols and' their salts frequently are not free from irritating and toxic effects upon the workmen who handle them or apply compositions containing them.

We have now discovered anew compound.

capryldinitrophenyl crotonate, which has distinct advantages over previously known compounds and which makes possible parasiticidal compositions which provide distinct improvement over compositions of the art. Although the new compound acts as a toxic agent against insects as both a stomach poison and as a contact poison, compositions containing it do not appear to cause ill effects on the workmen handling them. The advantage of fungicidal action in addition to the insecticidal action is rather unique and of considerable value. 'Yet, in spite Of the potency of the compositions containing capryldinitrophenyl crotonate, they are non-phytocidal and may be safely used on living plants.

Capryldinitrophenyl crotonate may be prepared from capryl alcohol, octanol-Z, and phenol through nitration and esterification. The reaction of capryl alcohol with phenol, as is known, may be effected in the presence of an acidic-condensing agent, such as acid clays or an organic sulfonic acid. To a solution of 1.03 kilograms of acid-condensed capryl phenol in 1.875 liters of ethylene dichloride, there. was slowly added over the course of 110 minutes at 1.125 kilograms of 70% nitric acid. The temperature was held at 25-35 C. After the acid had been added, the reaction mixture was stirred for one-half hour. It was then washed twice with water in a volume amounting to about half the volume of the re- 2 action mixture. The solvent was then evaporated while the mixture was heated on a water bath under reduced pressure. The residue consisted of capryldinitrophenol togther with some caprylmononitrophenol in the form of a dark-red viscous oil.

A solution of 2.08 kilograms of capryldinitrophenol was prepared with about one liter of petroleum ether (boiling range 60-100 C.) and thereto was added 610 grams of refined pyridine. The resulting solution was stirred, and thereto was added dropwise over the course of forty-five minutes 769 grams of crotonyl chloride. The reacting mixture was maintained at 29-46 C. with the aid of external cooling. Stirring was continued for another forty-five minutes and the mixture left standing for two days. About two liters of benzene was added and a solution of one kilogram of concentrated hydrochloric acid in five liters ofwater stirred thoroughly-therewith. The organic layerwas separated from the aqueous layer and washed successively with 5.5 liters of water, twice with 3.5 liters of normal sodium hydroxide solution, and twice with five liters of a solution containing 200 grams'of sodium chloride. The organic layer was then dried over anhydrous sodium sulfate and concentrated on a water bath under reduced pressure. The residue was a viscous dark-brown oil comprising 2.265 kilograms of technical capryldinitrophenyl crotonate.

Parasiticidal compositions comprising capryldinitrophenyl crotonate and a. carrier or diluent therefor are prepared by dispersing this compound in a finely divided, inert solid or dissolving it in an organic solvent. In either case, wetting agents or stickers may also be used. The new compound of thi invention may, furthermore, be supplemented with other toxicants, such as the arsenates, rotenone, pyrethrum, dichlorodiphenyl trichloroethane, dithiocarbamates, Bordeaux, and the like.

As a finely divided solid carrier, there may be used talc, clay, magnesium carbonate, diatomaceous earth, pyrophyllite, lignocellulosic flours, or the like, and mixtures of such solids. The capryldinitrophenyl crotonate may be ground with such a solid or may be impregnated on'such solid from a solution in a volatile solvent,=which is driven As solvents for the preparation of sprays, there may be used such organic materials as pine oil, cyclohexanol, other alcohols, and ether alcohols such as butoxyethanol, petroleum oils, vegetable oils, acetone, methyl ethyl ketone, dioxane, and

, bean beetle larvae.

' beetle.

1 part capryldinitrophenyl crotonat 48 parts alum sludge 48 parts lime 3 parts soya bean oil p 1 part capryldinitrophenyl crotonate 1 part spreader 98 parts talc 4 parts capryldinitrophenyl crotonate 86 parts talc parts fullers earth 1 part capryldinitrophenyl crotonate 1 part spreader-sticker 8 parts magnesium 'carbonate 8 parts clay 2 parts calcium silicate 2 parts capryldinitrophenyl crotonate 1 part octylphenoxydeca(ethoxy) ethanol 1 part pine oil parts capryldinitrophenyl crotonate 1 part octylphenoxydeca ethoxy ethanol 1 part condensed sodium naphthalene sulfonate 73 parts diatomaceous earth Dusts may preferably contain from about onehalf to ten per cent of capryldinitrophenyl crotonate, while sprays may desirably contain from 0.05% to 2% of this compound carried on a finely divided solid which is dispersed in water or emulsified in water with or without an added solvent. B

A spray was prepared from a solvent solution of capryldinitrophenyl crotonate as shown in Formula E above and diluted to one part of toxicant in eight hundred parts of water. This spray Was applied to bean plants infested with Mexican hours, a count was made. these larvae were dead.

A dust, prepared by grinding talc with capryl- At this time, 90% of dinitrophenyl crotonate and diluting with cla to hours.

This dust was applied to the confused flour A kill of 89% was obtained.

Test plots sprayed with a 0.25% concentration of capryldinitrophenyl crotonate carried on magnesium carbonate with a wetting agent and diluted with water showed excellent control of Colorado potato larvae and adults. The surprising At the end of twenty-four aftermath of this test, however, was the fact that when late blight killed many of the test plots under observation, those sprayed with capryldinitrophenyl crotonate remained green and free from blight. An increased yield of potatoes at the rate of one hundred bushels per acre was obtained over the untreated plots. An increase of fifty bushels per acre was obtained over plots treated with the usual copper-bearing sprays.

Sprays at 0.25% concentration of capryldinitrophenyl crotonate gave good to excellent control of armyworm, cabbage worm, cabbage looper, leafhoppers, and fleabeetles. At a concentration of 0.125%, this compound killed 97% of the bean beetle larvae on bean plants. Halving this concentration still permitted practical control of these larvae.

It was of considerable interest that the isomeric ester, di-isobutyldinitrophenyl crotonate, was markedly inferior to the ester of this invention against insects such as those listed. The isomer killed no carpet beetles, whereas capryldinitrophenyl crotonate gave fairly good control. The isomer was much less effective against cabbage looper, imported cabbage worm, armyworm, and other insects.

The crotonates which may be prepared as directed above are orthoand para-substituted in the phenyl ring. Thus, the esters may have the formula XO-O o o CH=OHCH3 where one X is a nitro group and the other is a capryl,

CaHis /'CH CH3 group.

The predominating isomer is the compound N02 OCOCH=CHCH3 CaHm CH CH:

We claim: An ester of the formula N01 -OCOCH=CHOH| CBHIQC JHCH' WILLIAM F. HESTER. W E CRAIG.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,073,316 Niederl 1 Mar. 9, 1937 2,127,090 Smith Aug. 16, 1938 2,192,197 Mills et al Mar. 5, 1940 2,384,306 Hester et al Sept. 4, 1945 2,437,527 Hester Mar. 9, 1948 

